Reagent for organic synthesis reaction containing organic triol borate salt

Abstract

[Problem] To provide an organoboron compound-containing reagent for organic synthesis reactions which undergoes no trimerization with dehydration, does not necessitate activation with a base, and is stable and highly active. [Means for Solving Problems] The reagent for organic synthesis reactions contains an organic triol borate salt represented by any of the general formulae (I) to (III) and general formula (XVI): (wherein R 1 represents alkyl, alkenyl, etc.; R 2 represents optionally substituted alkyl, alkenyl, alkynyl, etc. or represents hydrogen; m + represents an alkaline metal ion, phosphonium ion, or given ammonium ion; M 2+ represents an alkaline earth metal; X represents halogen or alkoxide; Y represents an alkali metal ion, etc.; A represents optionally substituted methylene; and n represents an integer).

1. A reagent for organic synthesis reaction comprising at least one among organic triol borate salts represented by the following general formulae (I) to (III) and (XVI): 
       
         
           
           
               
               
           
         
         wherein, R 1  represents alkyl group, alkenyl group, alkynyl group, aryl group or aralkyl group; R 2  represents alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group or heterocyclic group, which may have a substituent group, or hydrogen atom; R 4  represents a divalent aromatic hydrocarbon group or heterocyclic group, which may have a substituent group; m +  represents alkaline metal ion, phosphonium ion, or ammonium ion represented by general formula (IV): 
       
       
         
           
           
               
               
           
         
         wherein, R 3  represents an alkyl group); M 2+  represents an alkaline earth metal ion, X represents halogen or alkoxide; Y represents alkaline metal ion, phosphonium ion, ammonium ion represented by general formula (IV), or the group represented by general formula (XVII):
   MX ⊕   (XVII)
 
 
         wherein, M represents an alkaline earth metal, X represents halogen atom or alkoxide; A represents a methylene group which may have a substituent group; each n represents an integer of 1 to 10 and may be the same or the different, respectively. 
       
     
     
       2. The reagent for organic synthesis reaction according to  claim 1 , wherein n is 1 and A is a methylene group. 
     
     
       3. The reagent for organic synthesis reaction according to  claim 1 , wherein R 1  is methyl group, ethyl group or tert-butyl group. 
     
     
       4. The reagent for organic synthesis reaction according to  claim 1 , wherein R 4  is the group represented by general formula (XVIII): 
       
         
           
           
               
               
           
         
         (wherein, R 5  and R 6  represent each independently alkyl group), phenylene group or the group represented by the following formula (XIX): 
       
       
         
           
           
               
               
           
         
       
     
     
       5. The reagent for organic synthesis reaction according to  claim 1 , wherein the organic synthesis reaction using the aforesaid reagent for organic synthesis reaction is carbon-carbon bond formation reaction, carbon-nitrogen bond formation reaction, carbon-oxygen bond formation reaction or carbon-sulfur bond formation reaction. 
     
     
       6. The reagent for organic synthesis reaction according to  claim 1 , wherein the organic synthesis reaction using the aforesaid reagent for organic synthesis reaction is cross coupling reaction or addition reaction. 
     
     
       7. A cross coupling reaction method, which comprises reacting the reagent for organic synthesis reaction according to  claim 1  with organic halogenated compound, amine, alcohol or thioalcohol compound in the presence of palladium catalyst, nickel catalyst or copper catalyst. 
     
     
       8. An addition reaction method, which comprises reacting the reagent according to  claim 1  for organic synthesis reaction with the electron-withdrawing group substituted olefin compound, carbonyl compound or imine compound in the presence of rhodium catalyst or palladium catalyst. 
     
     
       9. An organic borate salt represented by the following general formulae (I) to (III) and (XVI): 
       
         
           
           
               
               
           
         
         wherein, R 1  represents alkyl group, alkenyl group, alkynyl group, aryl group or aralkyl group; R 2  represents alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group or heterocyclic group, which may have a substituent group or hydrogen atom; R 4  represents divalent aromatic hydrocarbon group or heterocyclic group, which may have a substituent group; m +  represents alkaline metal ion, phosphonium ion or ammonium ion represented by general formula (IV): 
       
       
         
           
           
               
               
           
         
         wherein, R 3  represents an alkyl group); M 2+  represents an alkaline earth metal ion, X represents halogen or alkoxide; Y represents alkaline metal ion, phosphonium ion, ammonium ion represented by general formula (IV), or the group represented by general formula (XVII):
   MX ⊕   (XVII)
 
 
         wherein, M represents an alkaline earth metal, X represents halogen atom or alkoxide; A represents a methylene group which may have a substituent group; each n represents an integer of 1 to 10 and may be the same or the different, respectively. 
       
     
     
       10. The organic triol borate salt according to  claim 9 , wherein n is 1, and A is a methylene group. 
     
     
       11. The organic triol borate salt according to  claim 9 , wherein R 1  is methyl group, ethyl group or tert-butyl group. 
     
     
       12. The organic triol borate salt according to  claim 9 , wherein R 2  is a heterocyclic group selected from the groups consisting of thienyl group, pyridyl group, thiophenyl group, furanyl group and pyrrolyl group, or alkynyl group. 
     
     
       13. The organic triol borate salt according to  claim 9 , wherein R 4  is the group represented by general formula (XVIII): 
       
         
           
           
               
               
           
         
         (wherein, R 5  and R 6  represent each independently alkyl group), phenylene group or the group represented by the following formula (XIX):